JP5571950B2 - Molecular sieve composition (EMM-10), production method thereof, and hydrocarbon conversion method using the composition - Google Patents

Description

  The present invention relates to a novel molecular sieve composition (EMM-10), a method for producing the same, and a method for converting hydrocarbons using the composition. In particular, the present invention relates to a novel MCM-22 type molecular sieve composition and a method for producing the same, and a method for converting hydrocarbons using the composition.

Traditionally, natural and synthetic molecular sieves are known to catalyze various hydrocarbon conversion reactions. Certain molecular sieves, zeolites, AIPO, and mesoporous materials are regular porous crystalline materials that have a well-defined crystal structure by X-ray diffraction (XRD). Inside the crystalline molecular sieve there are a number of voids interconnected by a number of channels or pores.
Within a particular molecular sieve, these multiple passages or holes are of uniform size. Such pore sizes adsorb molecules of a specific size, while molecules of larger dimensions do not adsorb, so such materials have become known as “molecular sieves” and are used in various industrial processes. It is used.

Such natural and synthetic molecular sieves include crystalline silicates containing various positive ions. Such a silicate is represented as a strong three-dimensional skeleton of SiO ₄ and an oxide of a group 13 element of the periodic table (for example, AlO ₄ ). The tetrahedral structure is cross-linked by sharing oxygen atoms, and the ratio of all Group 13 elements (for example, aluminum), silicon atoms, and oxygen atoms is 1: 2.
The ionic valence in the tetrahedral structure containing a Group 13 element (for example, aluminum) is balanced by including cations such as protons, alkali metals, and alkaline earth metal cations in the crystal. This is because the ratio of the Group 13 element (for example, aluminum) to various cations such as H ⁺ , Ca ²⁺ / 2, Sr ²⁺ / 2, Na ⁺ , K ⁺ , and Li ⁺ is 1: 1. Appears.

  The molecular sieve used for the catalyst includes naturally occurring or synthetic crystalline molecular sieve. Examples of such zeolites include large pore zeolites, intermediate diameter zeolites, and small diameter zeolites. These zeolites and their isotypes are described in W.W. H. Meier, D.C. H. Olson and Ch. Baerlocher et al., “Atlas of Zeolite Framework Types” (Elsevier, 5th edition, 2001).

Large pore zeolites generally have a pore size of at least about 7 mm and include zeolites with LTL, VFI, MAZ, FAU, OFF, * BEA, and MOR type frameworks (IUPAC Commission of Zeolite Nomenclature). Examples of large pore zeolites are mazzite, offretite, zeolite L, VPI-5, zeolite Y, zeolite X, omega, and beta.
In general, the intermediate diameter zeolite has a pore size of about 5 to less than about 7 mm, and includes, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON type framework zeolite (IUPAC Commission). of Zeolite Nomenclature). Examples of intermediate diameter zeolites also include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1, and silicalite 2.
The small-diameter zeolite has a pore size of about 3 to less than about 5.0 and includes, for example, CHA, ERI, KPI, LEV, SOD, and zeolites having an LTA type framework (IUPAC Commission of Zeolite Nomenclature). Examples of small diameter zeolites include ZK-4, ZSM-2, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, Examples include chabazite, zeolite T, gmelinite, ALPO-17, and clinoptilolite.

U.S. Pat. No. 4,439,409 discloses a crystalline molecular sieve composition of a substance called PSH-3 and a method for its production. In this production method, a hydrothermal reaction mixture containing hexamethyleneimine and an organic substance that acts as a structure-regulating agent in the synthesis of MCM-56 (US Pat. No. 5,362,697) is used. Hexamethyleneimine is also disclosed for use in the synthesis of crystalline molecular sieves MCM-22 (US Pat. No. 4,954,325) and MCM-49 (US Pat. No. 5,236,575).
A molecular sieve composition called zeolite SSZ-25 (US Pat. No. 4,826,667) is synthesized from a hydrothermal reaction mixture containing adamantane quaternary ammonium ions. US Pat. No. 6,077,498 discloses a crystalline molecular sieve composition called ITQ-1 and a method of synthesizing this composition from a hydrothermal reaction mixture containing one or more organic additives.

The term “MCM-22 type substance” (or “MCM-22 type substance” or “MCM-22 type molecular sieve”) as used herein includes the following molecular sieves.
(I) A molecular sieve composed of a common primary crystal unit cell “MWW skeletal topology molecular sieve”. (The unit cell is a three-dimensional arrangement of atoms and forms a crystal structure when placed in a three-dimensional space. Such a crystal structure is disclosed in “Atlas of Zeolite Framework Types (15th edition, 2001)”. And incorporated herein by reference.)
(Ii) a molecular sieve composed of a common secondary constituent unit, and when the unit cell of the MWW skeleton topology is placed in two dimensions, it becomes a “single layer of one unit cell thickness”, preferably the thickness is c—A molecular sieve that is one unit cell.
(Iii) A molecular sieve composed of a common secondary structural unit “a layer having a thickness of one or more unit cells”, wherein a layer having a unit cell thickness of more than 1 is a stack of at least two single layers of MWW skeleton topology Molecular sieves that are configured to be filled or combined. Such a laminated structure of secondary structural units may be regular, irregular, random, or a combination thereof.
(Iv) A molecular sieve in which unit cells having an MWW skeleton topology are combined in a two-dimensional or three-dimensional manner regularly or randomly.

MCM-22 type materials have lattice spacing d (d-spacing) peaks of 12.4 ± 0.25, 3.57 ± 0.07, and 3.42 ± 0.07% (calcined or It is characterized by having an X-ray diffraction pattern that is measured in an unpurified state after synthesis. MCM-22 type materials also have lattice spacing d peaks of 12.4 ± 0.25, 6.9 ± 0.015, 3.57 ± 0.07%, and 3.42 ± 0.07% (fired). Characterized by having an X-ray diffraction pattern in a measured or unpurified state.
X-ray diffraction data used for the analysis of molecular sieves can be obtained using an X-ray diffractometer equipped with a scintillation counter and a computer by standard methods using copper K-α double rays as incident radiation.
Substances belonging to the MCM-22 type material include MCM-22 (disclosed in US Pat. No. 4,954,325), PSH-3 (disclosed in US Pat. No. 4,439,409), SSZ-25 (US Pat. No. 4,826,667), ERB-1 (disclosed in European Patent No. 093032), ITQ-1 (disclosed in US Pat. No. 6,077,498), ITQ-2 (International Publication Pamphlet WO97 / ITQ-30 (disclosed in WO2005 / 118476), MCM-36 (disclosed in US Pat. No. 5,250,277), MCM-49 (disclosed in US Pat. No. 5,236,575). MCM-56 (disclosed in US Pat. No. 5,362,697) That. These patent documents are incorporated herein by reference.

  Compared with the conventional alkylation catalyst of large pore zeolite such as mordenite, the above-mentioned MCM-22 type molecular sieve has a 12-membered ring surface pocket, and this surface pocket is inside the molecular sieve. It is distinguished in that it does not communicate with the internal hole.

  Zeolite materials classified as MWW topology by IZA-SC are multi-layered materials with two pore systems, 10-membered and 12-membered rings. The aforementioned Atlas of Zeolite Framework Types classifies substances having this same topology into five different names. These are MCM-22, ERB-1, ITQ-1, PSH-3, and SSZ-25.

MCM-22 type molecular sieves can be used for various hydrocarbon conversion reactions. Examples of MCM-22 type molecular sieves are MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, and ERB-1. These molecular sieves can be used for aromatic alkylation.
For example, U.S. Pat. No. 6,936,744 discloses a process for producing monoalkylated aromatic compounds, particularly cumene, comprising at least partly comprising a polyalkylated aromatic compound and an alkylatable aromatic compound. Is contacted with an alkyl transfer catalyst in a liquid phase to form a monoalkylated aromatic compound, the alkyl transfer catalyst comprising at least two different crystalline molecular sieves, wherein the molecular sieves are zeolite beta, zeolite Peaks of lattice spacing d of Y, mordenite, and X-ray diffraction patterns are 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07, and 3.42 ± 0.07Å A method of selecting from appearing substances is disclosed.

S. H. Lee, C.I. H. Shin, S .; B. Hong et al., Chem. Lett. Vol.32, No. 6, 542-543 (2003), S.V. H. Lee, C.I. H. Shin, D.H. K. Yang, S .; D. Ahn, I .; S. Nam, S.M. B. Hong et al., Microporous and Mesoporous Materials, Vol. 68, 97-104 (2004), a hydrothermal reaction comprising water, Me ₆ -Diquat-5 dibromide, Ludox HS-40, anhydrous aluminum nitrate, and 50 wt% sodium hydroxide solution. MCM-22 molecular sieves synthesized by crystallization of the mixture have been reported. This mixture had the composition shown in Table 1. The mixture was crystallized under crystallization conditions (shown in Table 1) and found to be pure phase MCM-22 with a crystal size of about 0.5 × 0.05 μm (microplate form).

Crystal morphology, size, and agglomeration / agglomeration are known to affect catalyst behavior, particularly catalyst activity and stability.
Accordingly, there is a need for new molecular sieve compositions, particularly molecular sieve compositions of different morphologies, and methods for their production.

Solution

The present invention relates to a crystalline molecular sieve identified as EMM-10 in an ammonia exchanged or calcined form. The present invention also relates to a method for producing EMM-10.
In a preferred embodiment, EMMM-10 is an MCM-22 type molecular sieve.
In some embodiments, the present invention relates to unit molecular cells of MWW topology and relates to ammonia-exchanged or calcined forms of crystalline molecular sieves, wherein the crystalline molecular sieves are derived from an array of unit cells in the c-axis direction. Is identified by a diffraction streak. In another embodiment, the crystalline molecular sieve is identified by a curvilinear hk0 pattern of electron diffraction patterns.

In yet another embodiment of the invention, the crystalline molecular sieve is identified by a streak of unit cell diffraction in the c-axis direction. In yet another embodiment of the invention, the crystalline molecular sieve is identified by a double unit cell in the c-axis direction.
In yet another embodiment, the present invention relates to a crystalline MCM-22 molecular sieve having a total surface area of greater than 450 m ² / g as measured by nitrogen adsorption BET method. The crystalline MCM-22 type molecular sieve has an external surface area / total surface area ratio of less than 0.15 after conversion to H type by ion exchange with ammonium nitrate and calcination. Here, the external surface area is determined by a t-plot of the nitrogen adsorption BET method.

  In yet another embodiment, the invention relates to a crystalline molecular sieve in the form of a plate, wherein at least 50 wt% of the crystalline molecular sieve has a crystal diameter greater than 1 μm as measured by SEM.

  In some aspects, the crystalline molecular sieve is in the form of a plate, and at least 50 wt% of the crystalline molecular sieve has a crystal thickness of about 0.025 μm as measured by SEM.

In some embodiments, the invention relates to a method of producing a crystalline molecular sieve,
(A) at least one source of at least one tetravalent element (Y), at least one source of at least one alkali or alkaline earth element, and at least one structure-regulating agent (R); Supplying a mixture comprising water and optionally at least one source of at least one trivalent element (X), wherein the mixture has the following molar ratio:
Y: X ₂ = 10 to infinity, preferably 10 to 10,000, more preferably about 10 to 55;
H ₂ O: Y = 1 to 10,000, preferably about 5 to 35;
OH ⁻ when the trivalent element source is not corrected: Y = 0.001 to 0.59, and / or OH ⁻ when the trivalent element source is corrected: Y = 0.001 to 0.39;
M ⁺ : Y = 0.001 to 2, preferably about 0.1 to 1;
R: Y = 0.001 to 2, preferably about 0.1 to 1;
(Where M is an alkali metal and R is one of N, N, N, N′N′N′-hexamethyl-1,5-pentanediaminium salts (Me ₆ -Diquat-5 salts)), Preferably, R is dibrominated Me ₆ -Diquat-5, dichloride Me ₆ -Diquat-5, difluorinated Me ₆ -Diquat-5, diiodinated Me ₆ -Diquat-5, dihydroxide Me _6-. Diquat-5, sulfuric acid Me ₆ -Diquat-5, dinitrate Me ₆ -Diquat-5, hydrobromide Me ₆ -Diquat-5, hydroxide bromide Me ₆ -Diquat-5, hydrofluorinated Me ₆ - Daikuotto -5, hydroxide iodide Me ₆ - Daikuotto -5, hydroxide nitrate Me ₆ - Daikuotto -5, bromide fluoride Me ₆ - Daikuotto -5, fluoride chloride Me ₆ - Daikuotto -5, off Bromoiodide Me ₆ -Diquat-5, fluorinated nitric acid Me ₆ -Diquat-5, chlorobromide Me ₆ -Diquat-5, chloroiodinated Me ₆ -Diquat-5, chloronitrate Me ₆ -Diquat-5, iodide bromide Me ₆ - Daikuotto -5 bromide nitrate Me ₆ - is selected from the group consisting of Daikuotto -5, and mixtures thereof, more preferably, R dibromide Me ₆ - Daikuotto -5, two chloride Me ₆ - Daikuotto -5 difluoride Me ₆ - Daikuotto -5, two iodide Me ₆ - Daikuotto -5, dihydroxide Me ₆ - Daikuotto -5, sulfuric Me ₆ - Daikuotto -5, dinitrate Me ₆ - Daikuotto -5, and is selected from the group consisting of mixtures, and most preferably, R dibromide Me 6 _- a Daikuotto -5);
(B) producing a product containing the desired crystalline molecular sieve under crystallization conditions, wherein the temperature is from 100 ° C to 200 ° C, preferably from about 140 ° C to about 180 ° C; Including a crystallization time of about 1 hour to 400 hours, preferably about 1 to 200 hours, optionally with a stirring speed of 0 to 1000 RPM, preferably 0 to 400 RPM;
(C) recovering the crystalline molecular sieve;
(D) The recovered crystalline molecular sieve is
(1) ion-exchange the crystalline molecular sieve with an ammonium salt solution;
(2) firing the crystalline molecular sieve under firing conditions; or (3) treating the crystalline molecular sieve by ion exchange with an ammonium salt solution and firing under firing conditions. The present invention relates to a method for producing a crystalline molecular sieve.

In another embodiment, the present invention relates to a method for producing a crystalline molecular sieve,
(A) at least one source of at least one tetravalent element (Y), at least one source of at least one alkali or alkaline earth element, and at least one structure-regulating agent (R); Supplying a mixture comprising water and optionally at least one source of at least one trivalent element (X), wherein the mixture has the following molar composition ratio:
Y: X ₂ = 10 to infinity, preferably 10 to 10,000, more preferably about 10 to 55;
H ₂ O: Y = 1 to 10,000, preferably about 5 to 35;
OH ⁻ when the trivalent element source is not corrected: Y = 0.61 to 0.72, and / or OH ⁻ when the trivalent element source is corrected: Y = 0.041 to 0.49 or 0.51 to 0.62;
M ⁺ : Y = 0.001 to 2, preferably about 0.1 to 1;
R: Y = 0.001 to 2, preferably 0.1 to 1;
(Where M is an alkali metal and R is one of N, N, N, N′N′N′-hexamethyl-1,5-pentanediaminium salts (Me ₆ -Diquat-5 salts)), Preferably, R is dibrominated Me ₆ -Diquat-5, dichloride Me ₆ -Diquat-5, difluorinated Me ₆ -Diquat-5, diiodinated Me ₆ -Diquat-5, dihydroxide Me _6-. Diquat-5, sulfuric acid Me ₆ -Diquat-5, dinitrate Me ₆ -Diquat-5, hydrobromide Me ₆ -Diquat-5, hydroxide bromide Me ₆ -Diquat-5, hydrofluorinated Me ₆ - Daikuotto -5, hydroxide iodide Me ₆ - Daikuotto -5, hydroxide nitrate Me ₆ - Daikuotto -5, bromide fluoride Me ₆ - Daikuotto -5, fluoride chloride Me ₆ - Daikuotto -5, off Bromoiodide Me ₆ -Diquat-5, fluorinated nitric acid Me ₆ -Diquat-5, chlorobromide Me ₆ -Diquat-5, chloroiodinated Me ₆ -Diquat-5, chloronitrate Me ₆ -Diquat-5, iodide bromide Me ₆ - Daikuotto -5 bromide nitrate Me ₆ - is selected from the group consisting of Daikuotto -5, and mixtures thereof, more preferably, R dibromide Me ₆ - Daikuotto -5, two chloride Me ₆ - Daikuotto -5 difluoride Me ₆ - Daikuotto -5, two iodide Me ₆ - Daikuotto -5, dihydroxide Me ₆ - Daikuotto -5, sulfuric Me ₆ - Daikuotto -5, dinitrate Me ₆ - Daikuotto -5, and is selected from the group consisting of mixtures, and most preferably, R dibromide Me 6 _- a Daikuotto -5);
(B) producing a product containing the desired crystalline molecular sieve under crystallization conditions, wherein the temperature is from 100 ° C to 200 ° C, preferably from about 140 ° C to about 180 ° C; Including a crystallization time of about 1 hour to 400 hours, preferably about 1 to 200 hours, optionally with a stirring speed of 0 to 1000 RPM, preferably 0 to 400 RPM;
(C) recovering the crystalline molecular sieve;
(D) The recovered crystalline molecular sieve is
(1) ion-exchange the crystalline molecular sieve with an ammonium salt solution;
(2) firing the crystalline molecular sieve under firing conditions; or (3) treating the crystalline molecular sieve by ion exchange with an ammonium salt solution and firing under firing conditions. The present invention relates to a method for producing a crystalline molecular sieve.

In another embodiment, the present invention relates to a method for producing a crystalline molecular sieve,
(A) at least one source of at least one tetravalent element (Y), at least one source of at least one alkali or alkaline earth element, and at least one structure-regulating agent (R); Supplying a mixture comprising water and optionally at least one source of at least one trivalent element (X), wherein the mixture has the following molar composition ratio:
Y: X ₂ = 10 to infinity, preferably 10 to 10,000, more preferably about 10 to 55;
H ₂ O: Y = 1 to 10,000, preferably about 5 to 35;
OH ⁻ when the trivalent element source is not corrected: Y = 0.74 to 2 and / or OH ⁻ when the trivalent element source is corrected: Y = 0.64 to 2;
M ⁺ : Y = 0.001 to 2, preferably about 0.1 to 1;
R: Y = 0.001 to 2, preferably about 0.1 to 1;
(Where M is an alkali metal and R is one of N, N, N, N′N′N′-hexamethyl-1,5-pentanediaminium salts (Me ₆ -Diquat-5 salts)), Preferably, R is dibrominated Me ₆ -Diquat-5, dichloride Me ₆ -Diquat-5, difluorinated Me ₆ -Diquat-5, diiodinated Me ₆ -Diquat-5, dihydroxide Me _6-. Diquat-5, sulfuric acid Me ₆ -Diquat-5, dinitrate Me ₆ -Diquat-5, hydrobromide Me ₆ -Diquat-5, hydroxide bromide Me ₆ -Diquat-5, hydrofluorinated Me ₆ - Daikuotto -5, hydroxide iodide Me ₆ - Daikuotto -5, hydroxide nitrate Me ₆ - Daikuotto -5, bromide fluoride Me ₆ - Daikuotto -5, fluoride chloride Me ₆ - Daikuotto -5, off Bromoiodide Me ₆ -Diquat-5, fluorinated nitric acid Me ₆ -Diquat-5, chlorobromide Me ₆ -Diquat-5, chloroiodinated Me ₆ -Diquat-5, chloronitrate Me ₆ -Diquat-5, iodide bromide Me ₆ - Daikuotto -5 bromide nitrate Me ₆ - is selected from the group consisting of Daikuotto -5, and mixtures thereof, more preferably, R dibromide Me ₆ - Daikuotto -5, two chloride Me ₆ - Daikuotto -5 difluoride Me ₆ - Daikuotto -5, two iodide Me ₆ - Daikuotto -5, dihydroxide Me ₆ - Daikuotto -5, sulfuric Me ₆ - Daikuotto -5, dinitrate Me ₆ - Daikuotto -5, and is selected from the group consisting of mixtures, and most preferably, R dibromide Me 6 _- a Daikuotto -5);
(B) producing a product containing the desired crystalline molecular sieve under crystallization conditions, wherein the temperature is from 100 ° C to 200 ° C, preferably from about 140 ° C to about 180 ° C; Including a crystallization time of about 1 hour to 400 hours, preferably about 1 to 200 hours, optionally with a stirring speed of 0 to 1000 RPM, preferably 0 to 400 RPM;
(C) recovering the crystalline molecular sieve;
(D) The recovered crystalline molecular sieve is
(1) ion-exchange the crystalline molecular sieve with an ammonium salt solution;
(2) firing the crystalline molecular sieve under firing conditions; or (3) treating the crystalline molecular sieve with an ionic effect in an ammonium salt solution under firing conditions. The present invention relates to a method for producing a crystalline molecular sieve.

In another embodiment, the present invention relates to a method for producing a crystalline molecular sieve,
(A) at least one source of at least one tetravalent element (Y), at least one source of at least one trivalent element (X), and at least one at least one alkali or alkaline earth Supplying a mixture comprising an element source, at least one structure-regulating agent (R), and water, wherein the mixture has the following molar composition ratio:
Y: X ₂ = 10 to infinity, preferably 10 to 10,000, more preferably about 10 to 55;
H ₂ O: Y = 1 to 35, preferably 5 to 35;
OH ⁻ : Y = 0.001 to 2, preferably about 0.01 to 0.5;
M ⁺ : Y = 0.001 to 2, preferably about 0.1 to 1;
R: Y = 0.001 to 2, preferably about 0.1 to 1;
(Where M is an alkali metal and R is one of N, N, N, N′N′N′-hexamethyl-1,5-pentanediaminium salts (Me ₆ -Diquat-5 salts)), Preferably, R is dibrominated Me ₆ -Diquat-5, dichloride Me ₆ -Diquat-5, difluorinated Me ₆ -Diquat-5, diiodinated Me ₆ -Diquat-5, dihydroxide Me _6-. Diquat-5, sulfuric acid Me ₆ -Diquat-5, dinitrate Me ₆ -Diquat-5, hydrobromide Me ₆ -Diquat-5, hydroxide bromide Me ₆ -Diquat-5, hydrofluorinated Me ₆ - Daikuotto -5, hydroxide iodide Me ₆ - Daikuotto -5, hydroxide nitrate Me ₆ - Daikuotto -5, bromide fluoride Me ₆ - Daikuotto -5, fluoride chloride Me ₆ - Daikuotto -5, off Bromoiodide Me ₆ -Diquat-5, fluorinated nitric acid Me ₆ -Diquat-5, chlorobromide Me ₆ -Diquat-5, chloroiodinated Me ₆ -Diquat-5, chloronitrate Me ₆ -Diquat-5, iodide bromide Me ₆ - Daikuotto -5 bromide nitrate Me ₆ - is selected from the group consisting of Daikuotto -5, and mixtures thereof, more preferably, R dibromide Me ₆ - Daikuotto -5, two chloride Me ₆ - Daikuotto -5 difluoride Me ₆ - Daikuotto -5, two iodide Me ₆ - Daikuotto -5, dihydroxide Me ₆ - Daikuotto -5, sulfuric Me ₆ - Daikuotto -5, dinitrate Me ₆ - Daikuotto -5, and is selected from the group consisting of mixtures, and most preferably, R dibromide Me 6 _- a Daikuotto -5,
OH ⁻ : Y is calculated with or without correction of the trivalent element source);
(B) producing a product containing the desired crystalline molecular sieve under crystallization conditions, wherein the temperature is from 100 ° C to 200 ° C, preferably from about 140 ° C to about 180 ° C; Including a crystallization time of about 1 hour to 400 hours, preferably about 1 to 200 hours, optionally with a stirring speed of 0 to 1000 RPM, preferably 0 to 400 RPM;
(C) recovering the crystalline molecular sieve;
(D) The recovered crystalline molecular sieve is
(1) ion-exchange the crystalline molecular sieve with an ammonium salt solution;
(2) firing the crystalline molecular sieve under firing conditions; or (3) treating the crystalline molecular sieve by ion exchange with an ammonium salt solution and firing under firing conditions. The present invention relates to a method for producing a crystalline molecular sieve.

In one aspect, the crystalline molecular sieve of the present invention is an MCM-22 type molecular sieve.
In some embodiments, the invention relates to a method of producing a crystalline molecular sieve,
(A) at least one source of silicon, at least one source of at least one alkali or alkaline earth element, at least one structural regulator (R), water, and optionally at least one Mixing with an ammonium source to prepare a mixture with the following molar composition ratio:
Si: Al ₂ = 10 to infinity, preferably 10 to 10,000
H ₂ O: Si = 1 to 10,000, preferably 1 to 5000
OH ⁻ when not correcting the trivalent element source: Si = 0.001 to 0.59, and / or OH ⁻ : when correcting the trivalent element source (Si = 0.001 to 0.39)
M ⁺ : Si = 0.001 to 2
R: Si = 0.001 to 0.34, where M is an alkali metal and R is N, N, N, N′N′N′-hexamethyl-1,5-pentanediaminium (2 Brominated Me ₆ -Diquat-5).
(B) A step of producing a product containing the desired crystalline molecular sieve under crystallization conditions, wherein the temperature is 100 ° C. to 200 ° C. and the crystallization time is about 1 hour to 200 A step involving being time;
(C) recovering the crystalline molecular sieve;
(D) The recovered crystalline molecular sieve is
(1) ion-exchange the crystalline molecular sieve with an ammonium salt solution;
(2) firing the crystalline molecular sieve under firing conditions; or (3) treating the crystalline molecular sieve either by ion exchange with an ammonium salt solution and firing under firing conditions. The present invention relates to a method for producing a crystalline molecular sieve.

In some embodiments, the H ₂ O: Si molar ratio is in the range of about 5 to 35.

The invention further relates to a hydrocarbon conversion process,
(A) A step of contacting a hydrocarbon raw material with the crystalline molecular sieve of the present invention or the crystalline molecular sieve produced by the production method of the present invention under conversion conditions to produce a converted product.

  Various aspects of the invention will become apparent from the following detailed description, drawings, and claims.

1 is an X-ray diffraction pattern of an unpurified MCM-22 type molecular sieve of Example A. FIG.
FIG. 2 is an SEM image of the unpurified MCM-22 type molecular sieve of Example A.
FIG. 3 is an X-ray diffraction pattern of an unpurified MCM-22 type molecular sieve of Example 1.
4 is an SEM image of an unpurified MCM-22 type molecular sieve of Example 1. FIG.
FIG. 5 is an X-ray diffraction pattern of an unpurified MCM-22 type molecular sieve of Example 2.
6 is an SEM image of an unpurified MCM-22 type molecular sieve of Example 2. FIG.
FIG. 7 is an X-ray diffraction pattern of the MCM-22 type molecular sieve of Example 4 in an unpurified state (FIG. 7a), an ammonium ion exchanged state (FIG. 7b), and a fired state (FIG. 7c). It is.
FIG. 8 is an electron diffraction (ED) pattern of the calcined Example A sample, some phases of the calcined Example 4 sample, and most phases of the calcined Example 4 sample. Yes, FIG. 8a; Example A: FIG. 8b; Some components sharply similar to Example A: FIG. 8c; Main component of calcined Example 4 material (unrefined MCM-22 form of Example A) Implying a disordered layered structure of the electron diffraction pattern of the molecular sieve).
FIG. 9 shows the tilt series of (a) calcined Example A material; (b) unpurified Example A material; (c) calcined Example 4 material;

All patents, patent applications, test methods, prior literature, articles, publications, manuals, and other references cited in this application are hereby incorporated by reference to the extent they do not conflict with the application in their jurisdiction.
When the upper limit and the lower limit of a plurality of numerical values are described in the present application, all combinations of the lower limit and the upper limit are considered.
In the present application, the “skeleton type” is used in the meaning described in “Atlas of Zeolite Framework Types” (2001).
The element numbers in the periodic table of the present application are according to the example of Chemical and Engineering News, 63 (5), 27 (1985).

The “flat” form means a flat mineral having “thin plate-like crystals stacked in parallel”. The term “plate-like” form means thin plate-like crystals.
Those skilled in the art will recognize that MCM-22 type materials include amorphous materials, unit cells of non-MWW type skeletal topology (eg, MFI, MTW), and / or other impurities (eg, heavy metals and / or organic hydrocarbons). It will be understood that it contains impurities such as

  Examples of non-MCM-22 type molecular sieves coexisting in the MCM-22 type molecular sieve of the present invention are Kenyite, EU-1, ZSM-50, ZSM-12, ZSM-48, ZSM-5, ferrierite, mordenite. , Sodalite, and / or analcin.

  Examples of other non-MCM-22 type molecular sieves that coexist in the MCM-22 type molecular sieve of the present invention are molecular sieves having EUO, MTW, FER, MOR, SOD, ANA, and / or MFI type skeletons. is there. The MCM-22 type molecular sieve of the present invention is preferably substantially free of non-MCM-22 type molecular sieve.

  As used herein, “substantially free of non-MCM-22 type material” means that the MCM-22 type molecular sieve has a non-MCM-22 type (based on the total weight of impurities and pure MCM-22 type material phase). Impurities) are preferably contained in small amounts (less than 50 wt%), preferably less than 20 wt%.

The MCM-22 crystalline material has a composition in which the molar ratio is X ₂ O ₃ : (n) YO ₂ . Here, X is a trivalent element such as aluminum, boron, iron and / or gallium, preferably aluminum. Y is a tetravalent element such as silicon and / or germanium, and is preferably silicon. n is at least about 10, usually from about 10 to about 150, preferably from about 10 to about 60, more preferably from about 20 to about 40.
In an unpurified state, based on anhydrous crystals, this crystalline material is represented by the following formula for n moles of YO ₂ .
_{(0.005~l) M 2 O: (} l~4) R: X 2 O 3: nYO 2
Here, M is an alkali or alkaline earth metal, and R is an organic group. M and R are derived from materials used in the synthesis, are well known to those skilled in the art, and / or can be easily removed by post-treatment methods described in detail below.

In the detailed description of the invention, known analytical identification techniques were used to describe the molecular sieve material. These known techniques include the following analytical identification.
(A) Analysis of structure and crystallinity of molecular sieve material by X-ray diffraction (XRD).
(B) Measurement of the morphology and crystal size of the molecular sieve material with a scanning electron microscope.
(C) Chemical composition analysis by atomic absorption analysis and / or inductively coupled plasma mass spectrometry (ICP-MS or ICPMS).
(D) Measurement of adsorption capacity and surface area by Brunauer-Emmett-Teller (BET) method.
(E) Electron diffraction (ED). And / or (f) measurement of catalyst activity and catalyst stability by confirmation test.

<Powder Method X-ray Diffraction Pattern of Known MCM-22>
Known MCM-22 crystalline materials are distinguished from other crystalline materials by X-ray diffraction patterns.
The inner lattice spacing d was calculated in units of ridges. The relative line intensity I / Io was determined by using the profile fitting method (or second derivative), with the strongest line against the background being Io, 100.
Correction of the line intensity for the Lorentz effect and the polarization effect was not performed.
Relative line intensities are VS = very strong (> 60 to 100), S = strong (> 40 to 60), M = medium (> 20 to 40), and W = weak (0 to 20). Expressed in Even in diffraction data expressed as a single line, a plurality of lines may be partially or entirely overlapped when, for example, the crystal phase changes are different.

  In general, crystal phase changes include minor changes in unit cell constants without changes in crystal structure and / or changes in crystal symmetry. These minor effects include differences in cation content, including changes in relative line strength, differences in skeletal composition, differences in the degree of pore filling and packing properties, or the history of thermal and / or hydrothermal reactions. It can also be caused by differences. Other diffraction pattern differences indicate obvious material differences, and in the case of MCM-22, differences from other similar materials such as MCM-49, MCM-56, and PSH-3.

The lattice spacing d was determined to be broad when a peak width of about 1.5 degrees or more was observed at a half height defined as 50% from the baseline of the peak intensity to the maximum value.
The term “peak that can be discriminated by XRD” means a clear peak that is at least twice as strong as the average background noise level.

In this application, XRD “non-discrete” peaks (or “non-separated” peaks) mean that there is a monotonous portion between peaks (within the range of noise, successive points increase (or Constant), or decrease or become constant)).
XRD “discrete” peaks (or “separated” peaks) refer to XRD peaks that are not non-discrete (non-separated).

  This X-ray diffraction pattern is characteristic of all the crystalline compositions of the present application. The form of sodium and other forms of cation show substantially the same pattern, with slight shifts in the lattice spacing d and slightly different relative line intensities. Other minor differences can also occur due to the Y to X ratio (eg silicon to aluminum ratio) and the thermal history (eg firing).

  The crystalline molecular sieve composition of the present invention has peaks of lattice spacing d of 13.18 ± 0.25 and 12.33 ± 0.23 ± according to the X-ray diffraction pattern of the molecular sieve in an unpurified state ( Table 2), where the peak intensity of the 13.18 ± 0.25 peak is approximately equal to or greater than the peak intensity of the 12.33 ± 0.23 peak.

  The crystalline molecular sieve composition of the present invention further has peaks of lattice spacing d of 11.06 ± 0.18 and 9.25 ± 0.13 in the X-ray diffraction pattern of the molecular sieve in an unpurified state. (Table 3), where the peak intensity of the 11.06 ± 0.18 peak is approximately equal to or greater than the peak intensity of the 9.25 ± 0.13 peak.

In the crystalline molecular sieve composition of the present invention, the peaks at 11.06 ± 0.18 and 9.25 ± 0.13Å of the lattice spacing d of the molecular sieve in an unpurified state are non-separable peaks. It is characterized by
In this application, when the separation factor of two XRD peaks is referred to, the depression between the two peaks (the distance from the baseline to the lowest point between the two peaks) is the distance from the baseline to the line connecting the two peak vertices. It means the ratio obtained by dividing by the vertical distance.
Furthermore, when the crystalline molecular sieve composition of the present invention is baked, the crystalline molecular sieve composition has two lattice plane distances d of about 11 mm (2θ is about 8 degrees) and about 8.9 mm (2θ is about 10 degrees). Such XRD peaks are characterized by a separation factor of at least 0.4, preferably 0.5.

<Scanning electron microscope (SEM)>
FIG. 2 shows an SEM image of MCM-22 type molecular sieve manufactured by the method disclosed in US Pat. No. 4,954,325. The MCM-22 type molecular sieve produced by the method of US Pat. No. 4,954,325 exhibits a thin, relatively unclear hexagonal plate morphology, and the average diameter of the pieces observed by SEM is less than about 1 μm. is there. The average diameter of most small pieces is less than about 0.5 μm.
S. H. Lee, C.I. H. Shin, S .; B Hong et al., Chem. Lett. Vol. 32, no. The known unpurified MCM-22 crystalline material disclosed on pages 6,542-543 (2003) is reported to be in the form of small flakes with a particle size of about 0.5 × 0.05 μm. ing.

4 and 6 show SEM images of the crystalline molecular sieve of the present invention. The crystalline molecular sieves of the present invention (FIGS. 4 and 6) are mostly multilayer, preferably having at least 50 wt%, more preferably at least 75 wt% of crystalline molecular sieve crystals having a flat plate average diameter greater than 1 μm. It has a crystal form of a plate-like aggregate.
In addition, the crystalline molecular sieve of the present invention (FIGS. 4 and 6) preferably has a plate average of about 0.025 μm of the majority of the crystalline molecular sieve crystals, preferably at least 50 wt%, more preferably at least 75 wt%. It has a crystal form of a multilayer plate-like aggregate having a thickness.

<Surface area and adsorption amount>
The total surface area of the molecular sieve can be measured by the Brunauer-Emmett-Tellcr (BET) method using nitrogen adsorption-desorption (temperature of liquid nitrogen, 77 K). The internal surface area can be calculated from a t-plot of measurements by Brunauer-Emmett-Tellcr (BET) method. The external surface area can be calculated by subtracting the internal surface area from the total surface area measured by the Brunauer-Emmett-Tellcr (BET) method.

The crystalline molecular sieve (after calcination) of the present invention preferably has a total surface area (the sum of the external surface area and the internal surface area as measured by the BET method t-plot) of more than 450 m ² / g, preferably 475 m ² / g. Greater than, more preferably greater than 500 m ² / g.
Further, the crystalline molecular sieve (after firing) of the present invention has a value obtained by dividing the external surface area (measured by t-plot of BET method) by the total surface area, preferably less than 0.15, more preferably 0.13, More preferably, it is characterized by being less than 0.12.

<Electron crystal analysis>
Electron crystal analysis is an analysis method well known in the field of material chemistry. Regarding electron beam crystal analysis, it is incorporated by reference in this application. L. It is described in detail in Dorset, Structural Electron Crystallography (Plenum, New York, 1995).

The calcined MCM-22 type material (Comparative Example A), which is an example of a known unit cell, was hexagonal, space group P6 / mmm, a = about 14.21 Å, c = about 24.94 Å. .
When projected along the [001] axis, a sharp spot is observed in the hk0 pattern (FIG. 8A).
The amplitude data of a plurality of separated patterns for a lump of microcrystalline flakes satisfied the following relationship.
R = Σ || F (1) | −k | F (2) || / Σ | F (1) | ≦ 0.12
Here, k is normalized so that Σ | F (1) | = Σ | F (2) |, and | F (1) | and | F (2) | are comparisons of a plurality of separated patterns. The amplitude of the possible diffraction peak. A reciprocal lattice plot (FIG. 9a) with a tilt series of such a pattern shows that the spacing in the c-axis direction is approximately 25 mm.
On the other hand, a plot of the crystallite slope of a known MCM-22 precursor (Comparative Example A) (FIG. 9b) shows no lattice repetition in the c-axis direction (ie discontinuous reflection along c ^*). ), Showing a continuous streak of reflections.

  This result is consistent with the known Fourier transform of the single unit cell in the c-axis direction. The main hk0 electron diffraction pattern of the fired material of the present application is almost arc-shaped (FIG. 8C) in most cases, but is a spot pattern similar to the known MCM-22 material (Comparative Example A). A trace amount of impurities (compared to FIGS. 8B and 8A) was observed. The amplitude data of the pattern of a small number of spots was consistent with the known calcined MCM-22 material (R = 0.09). The arc-shaped pattern did not match very much (R = 0.14) even though the matching in the inside was good (R <0.12).

Applying phenomenological Lorentz correction to the new material to correct the arc-shaped reflection (R = 0.12) improved the consistency of these two patterns.
From the three-dimensional tilt of the fired material of the invention (Example 5, Fig. 9c), not only the reflection streaks along the c-axis (c ^* ), but also doubled cells repeated in this direction Was observed (see arrow in FIG. 9c).
The diffraction data of the crystalline molecular sieve of this invention (Example 5) shows that the structure of the basic unit cell of this material is the crystalline molecular sieve of the unit cell of a known calcined MCM-22 type material (Comparative Example A). It shows that it is not different from the structure of.

However, the crystalline molecular sieve of this invention (Example 5) differs from the crystalline molecular sieve of the known MCM-22 type material (Comparative Example A) in the following points.
(I) The layered structure of unit cells in the c-axis direction is broken so as to be supported by the streak of the diffraction pattern along the ( ^* c) direction in the arc-shaped hk0 pattern and / or the inclination of the microcrystal And / or (ii) c-doubled cells along the axial direction. On the other hand, the crystalline molecular sieve of the known MCM-22 type material (Comparative Example A) has a regular laminated structure along the c-axis direction and has regular crystallinity in all directions.
The electron diffraction pattern of the crystalline molecular sieve of this invention (Example 5) also confirms that the line is broad in the powder X-ray diffraction pattern.

<Formulation of hydrothermal reaction mixture>
Synthetic zeolites are prepared from aqueous hydrothermal reaction mixtures (or synthetic mixtures / synthetic gels) that contain the necessary oxides. In order to synthesize the zeolite of the desired structure, an organic structure control agent is included in the hydrothermal reaction mixture.
The use of structure-limiting agents is described by Lok et al. In an article entitled “The Role of Organic Moleculars in Molecular Sieve Synthesis” in “Zeolites, Vol. 3 (October 1983, pages 282-291)”.

After mixing the components of the hydrothermal reaction mixture, the hydrothermal reaction mixture is subjected to appropriate crystallization conditions. The crystallization conditions include raising the temperature of the hydrothermal reaction mixture, preferably with stirring. It may be preferred to age the hydrothermal reaction mixture at room temperature.
When the crystallization of the hydrothermal reaction mixture is complete, the crystalline product is recovered from the hydrothermal reaction mixture, in particular the liquid component of the hydrothermal reaction mixture. This recovery operation includes an operation of filtering the crystal and washing the crystal with water.

  However, in order to completely remove the hydrothermal reaction mixture residue from the crystals, it is calcined at a high temperature, for example 500 ° C., preferably in the presence of oxygen. This firing not only removes water from the crystal, but also decomposes and / or oxidizes the organic structural regulator that plugs the pores of the crystal that will become sites for ion exchange.

  The crystalline molecular sieve material of the present invention comprises an alkali or alkaline earth (M) such as sodium or potassium, a cation, an oxide X of a trivalent element such as aluminum, and an oxidation of a tetravalent element such as silicon. It is prepared from a hydrothermal reaction mixture containing the product Y, the organic structure regulating agent (R) described in detail below, and water. The hydrothermal reaction mixture has a composition in the following range, expressed as a molar ratio of oxides.

In these embodiments, when the reaction mixture for hydrothermal reaction has the composition shown in Table VI, the trivalent element source uncorrected OH ⁻ : YO ₂ molar ratio is about 0.001 to about 0.59. The OH ⁻ : YO ₂ molar ratio is in the range of about 0.001 to about 0.39.

The following OH ⁻ : YO ₂ molar ratio (without correction of trivalent element source) is useful for the OH ⁻ : YO ₂ molar ratio (without correction of trivalent element source) of these examples shown in Table VI. Lower limit values: 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, and 0.55.
The following OH ⁻ : YO ₂ molar ratio (without correction of trivalent element source) is useful for the OH ⁻ : YO ₂ molar ratio (without correction of trivalent element source) of these examples shown in Table VI. Upper limit values: 0.59, 0.55, 0.51, 0.5, 0.4, 0.3, 0.2, and 0.1.
The OH ⁻ : YO ₂ molar ratio (without correction of the trivalent element source) is preferably any one of the plurality of lower limit values and the plurality of upper limit values as long as the lower limit value is not more than the upper limit value. Within one of the ranges.
The OH ⁻ : YO ₂ molar ratio (without trivalent element source correction) is 0.001 to 0.59, alternatively 0.01 to 0.5, alternatively 0.1 to 0.5, in one embodiment, In another embodiment 0.1 to 0.4.

The following OH ⁻ : YO ₂ molar ratio (with trivalent element source correction) is useful for the OH ⁻ : YO ₂ molar ratio (with trivalent element source correction) of these examples shown in Table VI. Lower limits: 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.3, and 0.35.
The following OH ⁻ : YO ₂ molar ratio (with trivalent element source correction) is useful for the OH ⁻ : YO ₂ molar ratio (with trivalent element source correction) of these examples shown in Table VI. Upper limit values: 0.39, 0.35, 0.31, 0.3, 0.2, and 0.1.
The OH ⁻ : YO ₂ molar ratio (with correction of the trivalent element source) is preferably any one of the plurality of lower limit values and the plurality of upper limit values as long as the lower limit value is not more than the upper limit value. Within one of the ranges.
The OH ⁻ : YO ₂ molar ratio (with trivalent element source correction) is 0.001 to 0.39, alternatively 0.01 to 0.35, alternatively 0.1 to 0.3, in one embodiment, In another embodiment, it is 0.1 to 0.25.

  The crystalline molecular sieve material of the present invention includes, for example, an alkali or alkaline earth (M) such as sodium or potassium, a cation, an oxide X of a tetravalent element such as aluminum, and a tetravalent element such as silicon. Prepared from a hydrothermal reaction mixture containing the oxide Y, an organic structure-regulating agent (R) described in detail below, and water. The hydrothermal reaction mixture has a composition in the following range, expressed as a molar ratio of oxides.

In these embodiments, when the reaction mixture for hydrothermal reaction has the composition shown in Table VII, the trivalent element source uncorrected OH ⁻ : YO ₂ molar ratio ranges from about 0.74 to about 2. The OH ⁻ : YO ₂ molar ratio with and / or with the correction of the trivalent element source ranges from about 0.64 to about 2.

The following OH ⁻ : YO ₂ molar ratio (without correction of trivalent element source) is a useful lower limit of the OH ⁻ : YO ₂ molar ratio (without correction of trivalent element source) of the production method of the present application. : 0.74, 0.77, 0.78, 0.80, 0.90, 1, and 1.5.
The following OH ⁻ : YO ₂ molar ratio (without correction of trivalent element source) is a useful upper limit of the OH ⁻ : YO ₂ molar ratio (without correction of trivalent element source) of the production method of the present application. : 2, 1.6, 1.4, 1.3, 1.2, 1, 0.9, and 0.8.
The OH ⁻ : YO ₂ molar ratio (without correction of the trivalent element source) is preferably any one of the plurality of lower limit values and the plurality of upper limit values as long as the lower limit value is not more than the upper limit value. Within one of the ranges.
The OH ⁻ : YO ₂ molar ratio (without correction of the trivalent element source) is 0.74 to 2, alternatively 0.8 to 2, alternatively 0.8 to 1, in one embodiment, 0 in another embodiment. .8 to 1.1.

The following OH ⁻ : YO ₂ molar ratio (with correction of trivalent element source) is a useful lower limit of the OH ⁻ : YO ₂ molar ratio (with correction of trivalent element source) of the production method of the present application. : 0.64, 0.65, 0.66, 0.7, 0.75, 0.80, 0.90, 1, and 1.5.
The following OH ⁻ : YO ₂ molar ratio (with correction of trivalent element source) is a useful upper limit of the OH ⁻ : YO ₂ molar ratio (with correction of trivalent element source) of the production method of the present application. : 2, 1.6, 1.4, 1.3, 1.2, 1, 0.9, and 0.8.
The OH ⁻ : YO ₂ molar ratio (with correction of the trivalent element source) is preferably any one of the plurality of lower limit values and the plurality of upper limit values as long as the lower limit value is not more than the upper limit value. Within one of the ranges.
The OH ⁻ : YO ₂ molar ratio (with trivalent element source correction) is 0.74 to 2, or 0.8 to 2, or 0.8 to 1, in one embodiment, and 0 in another embodiment. .8 to 1.1.

  The crystalline molecular sieve material of the present invention includes, for example, an alkali or alkaline earth (M) such as sodium or potassium, a cation, an oxide X of a tetravalent element such as aluminum, and a tetravalent element such as silicon. Prepared from a hydrothermal reaction mixture containing the oxide Y, an organic structure-regulating agent (R) described in detail below, and water. The hydrothermal reaction mixture has a composition in the following range, expressed as a molar ratio of oxides.

  Various elements contained in the final product may be derived from commercial products or disclosed in publicly known literature. The preparation of the synthesis mixture is similar.

Y is a tetravalent element selected from Groups 4 to 14 of the periodic table, for example, silicon and / or germanium, preferably silicon. In some embodiments of the present invention, in order to obtain a crystalline product of the present invention, the source of YO ₂ is YO 2 _solid, preferably YO ₂ to about 30 wt% solids.
When YO ₂ is silica, in the formation of crystals from the above mixture, preferably a silica source containing about 30 wt% solid silica, such as Aerosil or UItrasil (deposition containing about 90 wt% silica, from Degussa, Silica sold under spray dried silica) or trade name Ludox, for example from Grace Davison, or HiSil (about 87 wt% silica, about 6 wt% free H ₂ O, about 4.5 wt% hydrated bound water It is preferable to use an aqueous colloidal suspension of silica sold in the form of precipitated hydrated SiO ₂ ) having a particle size of about 0.02 μm.

That is, preferably the YO ₂ , eg silica source, contains about 30 wt% solid YO ₂ , eg silica, preferably about 40 wt% solid YO ₂ , eg silica. The silicon source may also be a silicate, such as an alkyl metal silicate, or a tetraalkylorthosilicate.

In another embodiment of the invention, the YO ₂ source comprises a tetravalent element (Y) acid. When YO ₂ is silicon, the silicon source is an acid containing silicon.

X is a trivalent element selected from Groups 3 to 13 of the periodic table, for example, aluminum and / or boron and / or iron and / or gallium, and preferably aluminum. The source of X ₂ O ₃ , such as aluminum, is aluminum sulfate or hydrated alumina. Other aluminum sources include, for example, other water-soluble aluminum salts, sodium aluminate, or alkoxides such as isopropoxyaluminum, or chip-like metallic aluminum.

As the alkali or alkaline earth metal element, lithium, sodium, potassium, calcium, and magnesium are preferable. The source of the alkali or alkaline earth metal element is preferably a metal oxide, a metal chloride, a metal fluoride, a sulfated metal, a nitrated metal, or a metal aluminate. The sodium source is preferably sodium hydroxide or sodium aluminate. Further, the alkali metal is bonded to ammonium ion (NH ⁴⁺ ) or an equivalent thereof, such as an alkyl ammonium ion.

In some embodiments of the invention, the molar ratio of M: YO ₂ , eg, M: SiO ₂ , has a lower limit of 0.001, preferably 0.01, preferably 0.1, and an upper limit of 2.0. , Preferably in the range of 1, preferably 0.5. The molar ratio of M: YO ₂ , for example, M: SiO ₂ , is preferably in a range in which any one of the plurality of lower limit values is combined with any one of the plurality of upper limit values.

In some embodiments of the invention, the molar ratio of H ₂ O: YO ₂ , eg H ₂ O: SiO ₂ , has a lower limit of 1, preferably 5, preferably 10, and an upper limit of 10,000, preferably 5000. , Preferably in the range of 500. The molar ratio of H ₂ O: YO ₂ , for example, H ₂ O: SiO ₂ , is preferably within a range in which any one of the plurality of lower limits is combined with any one of the plurality of upper limits. is there.

The OH ⁻ : YO ₂ molar ratio of this invention (without correction of trivalent element source) does not include correction of acid in the hydrothermal reaction mixture. The OH ⁻ : YO ₂ molar ratio (without correction of the trivalent element source) is the total number of hydroxyl groups added to the hydrothermal reaction mixture, and the total number of Y elements added to the hydrothermal reaction mixture. It is determined by dividing by the number of moles.

The hydroxyl (OH ⁻ ) source is preferably an alkyl metal oxide such as Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O, Fr ₂ O, or combinations thereof; ammonium hydroxide, Alkyl earth metal oxides such as BeO, MgO, CaO, SrO, BaO, RaO, or combinations thereof; alkyl earth metal hydroxides such as Be (OH) ₂ , Mg (OH) ₂ , Ca (OH ) ₂ , Sr (OH) ₂ , Ba (OH) ₂ , Ra (OH) ₂ , or combinations thereof; oxides or hydroxides of elements selected from Group 3 to 17; or combinations thereof; organic A hydroxide, for example, quaternary ammonium hydroxide, a hydroxide of an organic structure regulator (R) used for synthesis.

In the present invention, the OH ⁻ : YO ₂ molar ratio (with correction of trivalent element source) includes correction of the amount of acid in the reaction mixture for hydrothermal reaction.
The number of moles of OH ⁻ after correction is 3 times the number of moles of a trivalent element (when a trivalent element source is supplied in the form of a salt other than an oxide, hydroxide, or metal) It is obtained by subtracting from the total number of moles of hydroxyl groups added to the reaction mixture for reaction.
Accordingly, the OH ⁻ : YO ₂ molar ratio (with trivalent element source correction) is calculated by dividing the total number of hydroxyl groups after correction by the total number of Y elements added to the reaction mixture for hydrothermal reaction. Is required.

In some embodiments of the invention, the OH ⁻ : YO ₂ molar ratio, eg, OH ⁻ : SiO ₂ molar ratio, has a lower limit of 0.001, preferably 0.01, or 0.1, and an upper limit of 2.0, preferably 1 or 0.5. The OH ⁻ : YO ₂ molar ratio, such as the OH ⁻ : SiO ₂ molar ratio, is within the range of a combination of any of the above lower limits and any of the above upper limits.

The structure directing agent R is at least one of N, N, N, N′N′N′-hexamethyl-1,5-pentanediaminium salt (Me ₆ -Diquat-5 salts), for example, water Oxidized, chlorinated, brominated, fluorinated, nitrated, sulfated, phosphorylated Me ₆ -Diquat-5, and mixtures thereof.

In some embodiments, structure-directing agent R is dibromide Me ₆ - Daikuotto -5, dichloride Me ₆ - Daikuotto -5 difluoride Me ₆ - Daikuotto -5, Two iodide Me ₆ - Daikuotto - 5, dihydroxylated Me ₆ -Diquat-5, sulfuric acid Me ₆ -Diquat-5, dinitrate Me ₆ -Diquat-5, hydrobromide Me ₆ -Diquat-5, hydroxide bromide Me ₆ -Diquat- 5, Hydrofluorinated Me ₆ -Diquat-5, Hydroiodinated Me ₆ -Diquat-5, Hydroxynitric acid Me ₆ -Diquat-5, Fluorobromide Me ₆ -Diquat-5, Fluorochloride Me ₆ -Diquat-5, fluoriodinated Me ₆ -Diquat-5, fluorinated nitric acid Me ₆ -Diquat-5, Chlorobromide Me ₆ -Diquat-5, Chloroiodide Me ₆ Selected from the group consisting of: diquat-5, nitric chloride Me ₆ -diquat-5, iodobrominated Me ₆ -diquat-5, brominated nitric acid Me ₆ -diquat-5, and mixtures thereof.

A factor that affects the cost and quality of the synthetic crystalline molecular sieve is the amount of structure-directing agent used (R: YO ₂ , eg, R: SiO ₂ molar ratio). In general, structure-directing agents are the most expensive of most crystalline molecular sieve hydrothermal reaction mixtures. The smaller the amount of structure directing agent in the hydrothermal reaction mixture (lower R: YO ₂ ratio, eg, lower R: SiO ₂ molar ratio), the lower the molecular sieve that is the final product.

In some embodiments of the invention, the R: YO ₂ , eg, R: SiO ₂ molar ratio has a lower limit of 0.001, preferably 0.05, or 0.1 and an upper limit of 2.0. , Preferably 0.5 or 0.15.
R: YO ₂ , for example, R: SiO ₂ molar ratio is within the range of combinations of any of the above lower limits and any of the above upper limits.

  The hydrothermal reaction mixture is supplied from one or more sources. The hydrothermal reaction mixture may be prepared in batch or continuously. The crystal size and crystallization time of the crystalline material of the present invention vary depending on the properties of the hydrothermal reaction mixture used and the crystallization conditions.

  For those skilled in the art, a synthetic mixture having a composition within the above molar ratio range is one in which the synthetic mixture is made by mixing, adding, reacting, or other means of preparing such a mixture, It will be understood that this means that it has a composition within the above molar ratio range.

  Articles made by mixing, adding, reacting, or other means of preparing this type of mixture may or may not contain each component as prepared. Products made by mixing, adding, reacting, or other means of preparing this kind of mixture were prepared by means of mixing, adding, reacting, or other means of preparing such a mixture. Sometimes, the reaction product of each component is included.

  Optionally, seed crystals can be included in the hydrothermal reaction mixture. When seed crystals are used in the molecular sieve hydrothermal reaction mixture, for example, control of the particle size of the product, elimination of the use of organic template molecules, acceleration of the synthesis reaction, increase in the proportion of the desired skeletal structure in the product It is well known that there are various advantages.

In some embodiments of the invention, the crystalline molecular sieve is synthesized from 0 to about 25 wt%, preferably from about 1 to 5 wt%, based on the total weight of the tetravalent elemental oxide (eg, silica) of the hydrothermal reaction mixture. % In the presence of seed crystals.
Seed crystals are provided from synthetic reactions similar to those in which they are used. In general, any form of crystals can be used to promote a new synthesis reaction.

<Crystalling conditions>
Crystallization of the crystalline molecular sieve of the present invention can be carried out under stirring or static conditions in a reaction vessel such as an autoclave. A suitable temperature range for crystallization is from about 100 ° C. to about 200 ° C., for a time sufficient to cause crystallization at that temperature, for example from about 1 hour to about 400 hours, optionally from 0 to 1000 revolutions per minute ( RPM).
Preferably, the temperature range for crystallization is about 140 to about 180 ° C., and sufficient time to cause crystallization at that temperature is about 1 to 200 hours, optionally stirring at 0 to 400 RPM.

  Thereafter, the crystals are separated from the liquid and recovered. This production method includes a aging period at room temperature (˜25 ° C.) or preferably at a lower temperature than the hydrothermal reaction before the high-temperature hydrothermal reaction treatment (hydrothermal reaction). The hydrothermal reaction includes a period in which the temperature is changed continuously or stepwise.

  Optionally, the hydrothermal reaction can be carried out using various stirring means such as stirring or rotating the container around a horizontal axis (tumbling). The agitation speed is in the range of 0 to about 1000 RPM, preferably 0 to about 400 RPM.

  In certain embodiments, the crystalline molecular sieve of the present invention is a MCM-22 type material. In preferred embodiments, the crystalline molecular sieve of the present invention comprises at least MCM-22, MCM-49, MCM-56, MCM-22, and / or MCM-49, and / or MCM-56, at least. Any one type.

  The synthesized molecular sieve is filtered off, washed with water and / or dried. Crystallized crystalline molecular sieve is recovered and further ion exchange with ammonium salts (eg, ammonium hydroxide, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, or combinations thereof) and / or a temperature of 200 Calcination in an oxidizing atmosphere (for example, in air, in a gas in which the partial pressure of oxygen exceeds 0 kPa-a), etc. Processing is performed.

<Catalysis and adsorption>
The production, modification and properties of molecular sieves and / or zeolites are described in “Molecular Sieves—Principles of Synthesis and Identification (R. Szostak, Blackie Academic & Professional, London 1998, Second Edition, London, Rem. In addition to sieves, amorphous materials, mainly silica, aluminum silicate, and aluminum oxide, have been used in adsorbents and catalyst supports.

Spray drying, spheronization, pelletizing to form catalysts, adsorbents, and microporous or other types of porous materials for ion exchange into, for example, spherical particles, extruded shapes, pellet shapes, and tablet shapes Molding methods such as extrusion have been used and are still used.
These molding methods are described in “Catalyst Manufacture” (AB Styles, TA Koch, Marcel Dekker, New York, 1995).

  If desired, at least a portion of the metal cations in the as-manufactured material can be ion exchanged with other cationic species by known techniques. Preferred exchange cations include metal ions, hydrogen precursors, eg hydrogen precursors such as ammonium ions, and mixtures thereof. Particularly preferred cations are those that impart a catalytic action suitable for a given hydrocarbon conversion reaction. These include hydrogen, rare earth metals, Group 1-17 metals of the periodic table, preferably Group 2-12 metals.

When the crystalline molecular sieve of the present invention, preferably MCM-22 type molecular sieve is used as an adsorbent or a catalyst for the conversion reaction of an organic compound, at least a part thereof must be dehydrated.
Dehydration can be carried out by heating the crystalline material in an air or nitrogen atmosphere at atmospheric pressure, reduced pressure, or increased pressure to a temperature in the range of 200 ° C. to 595 ° C. for 30 minutes to 48 hours. The degree of dehydration can be measured by the weight loss percentage with respect to the total weight loss of the molecular sieve sample after passing dry nitrogen (water partial pressure less than 0.001 kPa) at 595 ° C. for 48 hours.
Dehydration can be carried out by placing the silicate in vacuum at room temperature (25 ° C.), but it takes time to sufficiently dry.

  When the crystalline molecular sieve of this invention, preferably MCM-22 type molecular sieve, is used as a catalyst, the heat treatment removes part or all of the organic components. The crystalline molecular sieve of this invention, preferably the MCM-22 type molecular sieve, is a catalyst in combination with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium. Used for hydrogenation-dehydrogenation.

  These hydrogenation components are introduced into the molecular sieve material by co-crystallization, for example by exchanging, impregnating or physically mixing Group 13 elements such as aluminum in the molecular sieve structure. The When the hydrogenation component is platinum, for example, the silicate can be impregnated into the molecular sieve by treating with a solution containing platinum ions. Suitable platinum compounds in such cases include chloroplatinic acid, platinum chloride, various compounds including platinum and amine complexes, and the like.

The crystalline molecular sieves, preferably MCM-22 type molecular sieves, can be converted to other forms by heat treatment, especially when in the hydrogenated, ammoniumated, metallized form. The heat treatment is generally performed by heating the molecular sieve in any of these forms at a temperature of at least 370 ° C. for at least 1 minute, usually not exceeding 1000 hours.
Although the heat treatment can be performed under reduced pressure, it is preferably performed under atmospheric pressure for ease of operation. The heat treatment is performed at a maximum temperature of 925 ° C. The heat-treated molecular sieve is particularly preferably used as a catalyst for several hydrocarbon conversion reactions. The heat-treated molecular sieve is suitably used as a catalyst for several organic reactions, such as a catalyst for hydrocarbon conversion, especially when in hydrogenated, ammoniumated or metallized form.

Non-limiting examples of such reactions include U.S. Pat. Nos. 4,954,325, 4,973,784, 4,992,611, 4,956,514, 4,962, No. 250, No. 4,982,033, No. 4,962,257, No. 4,962,256, No. 4,992,606, No. 4,954,663, No. 4,992,615 4,983,276, 4,982,040, 4,962,239, 4,968,402, 5,000,839, 5,001,296, 4,986,894, 5,001,295, 5,001,283, 5,012,033, 5,019,670, 5,019,665, 5, No. 019,664 and 5,013,422 And the like. These documents are incorporated herein by reference.
The crystalline molecular sieve produced according to the present invention is shaped into various shapes of particles. In general, the particles are in the form of a molded product such as a powder, granule or extruded shape. When the molecular sieve catalyst is formed into an extruded shape or the like, the molecular sieve catalyst is partially or completely dried before extrusion and then extruded.

The crystalline molecular sieve of this invention, preferably the MCM-22 type molecular sieve, can also be used as an adsorbent. For example, it can be used to separate at least one component from a mixture of multiple components that are in the gas phase or in the liquid phase and have different adsorption properties for the crystalline molecular sieve of the present invention.
That is, by bringing a mixture of a plurality of components into contact with the crystalline molecular sieve of the present invention capable of selectively adsorbing one component, a plurality of components having different adsorption characteristics with respect to the crystalline molecular sieve of the present invention. At least one component can be partially or substantially completely separated from the mixture.

The crystalline molecular sieve of this invention, preferably MCM-22 type molecular sieve, is useful as a catalyst for various processes including separation processes and hydrocarbon conversion processes.
Of the hydrocarbon conversion process wherein the crystalline molecular sieve of the present invention, preferably MCM-22 type molecular sieve alone, or a combination of one or more other catalytically active materials including other crystalline catalysts exhibits catalytic activity. Examples include the following processes:

(I) a process of alkylating aromatic hydrocarbons such as benzene with long chain olefins such as C ₁₄ olefins, the reaction conditions including a temperature of about 340 ° C. to about 500 ° C., a pressure of about 101 to about 20200kPa-a (absolute pressure), a weight hourly space velocity from about ^{2 hr -1} to about 2000 hr ^-1, include any one or a combination of aromatic hydrocarbon / olefin mole ratio of from about 1/1 to about 20/1, which Produces an aromatic having a long chain alkyl group, and the aromatic having the long chain alkyl group is then sulfonated to provide a synthetic detergent.
(Ii) a process of alkylating an aromatic hydrocarbon with a gas phase short chain olefin, such as alkylating benzene with propylene to produce cumene, the reaction conditions being a temperature of about 10 ° C. to about 125 ° C., Any one or a combination of pressures from about 101 to about 3030 kPa-a, a weight hourly space velocity (WHSV) of aromatic hydrocarbons from about 5 hr ⁻¹ to about 50 hr ⁻¹ are included.
The (iii) reformate comprising benzene and toluene was alkylated with fuel gas containing C ₅ olefins, comprising especially mono-, and process for producing the dialkylated product, the reaction conditions, a temperature of about 315 ° C. about 455 ° C. from the pressure from about 3000 to about 6000 kPa-a, about the WHSV to about 0.4hr ^-1 olefin 0.8Hr ^-1, about the WHSV to about ^{1hr -1} of reformulated gasoline ^{2 hr -1,} and supplies Any one or combination of gas recycling rates of 1.5 to 2.5 vol / vol to fuel gas is included.
(Iv) such as benzene, toluene, xylene, aromatic hydrocarbons such as naphthalene, for example by alkylation with long chain olefins, such as C ₁₄ olefins, in the process of providing a lubricating oil feed of alkylated aromatic hydrocarbons The reaction conditions include any one or combination of a temperature of about 160 ° C. to about 260 ° C. and a pressure of about 2600 to about 3500 kPa-a.
(V) a process in which phenol is alkylated with an olefin or equivalent alcohol to provide a long chain alkylphenol, the reaction conditions include a temperature of about 200 ° C. to about 250 ° C., a pressure of about 1500 to about 2300 kPa-a, total Any one or combination of WHSV from about 2 hr ⁻¹ to about 10 hr ⁻¹ is included.
(Vi) A process for converting light paraffins to olefins and aromatic hydrocarbons, wherein the reaction conditions include a temperature of about 425 ° C. to about 760 ° C., a pressure of about 170 to about 15000 kPa-a, any one or a combination Is included.
(Vii) a process for converting light olefins to hydrocarbons equivalent to gasoline, distilled oil, or lubricating oil, and the reaction conditions include a temperature of about 175 ° C. to about 375 ° C. and a pressure of about 800 to about 15000 kPa-a. Or one or a combination.
(Viii) a two-stage hydrocracking process for upgrading a hydrocarbon feedstock with an initial boiling point greater than about 260 ° C. to a product having a boiling range equivalent to distilled oil and gasoline, wherein the MCM of the present invention is The product is used in combination with a -22 type molecular sieve and a group 8-10 metal, and this product is used in the second stage in combination with a zeolite beta group 8-10 metal in the catalyst. Temperature of about 340 ° C. to about 455 ° C., pressure of about 3000 to about 18000 kPa-a, hydrogen circulation rate of about 176 to about 1760 liters / liter, liquid space velocity (LHSV) of about 0.1 hr ⁻¹ to about 10 hr ⁻¹ One or a combination is included.
(Ix) a process of combined hydrocracking and dewaxing in the presence of an MCM-22 type molecular sieve of the invention and a hydrogenation component catalyst, or in the presence of such a catalyst and zeolite beta, The conditions include a temperature of about 350 ° C. to about 400 ° C., a pressure of about 10,000 to about 11000 kPa-a, an LHSV of about 0.4 hr ⁻¹ to about 0.6 hr ⁻¹ , and a hydrogen circulation rate of about 528 to about 880 liters / liter. Any one or combination is included.
(X) reacting alcohol and olefin under conversion conditions, for example by reacting methanol with isobutene and / or isopentene to produce methyl-butyl ether (MTBE) and / or t-amyl methyl ether (TAM). The reaction is carried out under conditions of a temperature of about 20 ° C. to about 200 ° C., a pressure of about 200 to about 20000 kPa-a, a WHSV (gram olefin / hr gram zeolite) of about 0.1 hr ⁻¹ to about 200 hr ^−1. , Any one or combination of olefin feed molar ratios to alcohol of about 0.1 / 1 to about 5/1.
(Xi) A process of disproportionating toluene in the presence of C ₉ + aromatic, wherein the reaction conditions include a temperature of about 315 ° C. to about 595 ° C., a pressure of about 101 to about 7200 kPa-a, hydrogen / hydrocarbon mol to about 0 (hydrogenated no addition) to about 10, WHSV of about 0.1 hr ^-1 to about 30 hr ^-1 ratio include any one or combination.
(Xii) Reaction for synthesizing 2- (4-isobutylphenyl) propionic acid having medical activity, i.e., ibuprene, by reacting isobutylbenzene and propylene oxide to produce intermediate 2- (4-isobutylphenyl) propanol And then the alcohol is oxidized to the corresponding carboxylic acid.
(Xiii) A process for producing a dye by reacting a heterocyclic compound that reacts with a fiber and an amine, which is substantially salt-free as in DE 3,625,693, which is incorporated herein by reference. Used as an acid binder in the process of producing reactive dyes.
(Xiv) an adsorbent that separates 2,6-toluene diisocyanate (2,6-TDI) from isomers of TDI, as in US Pat. No. 4,721,807, which is incorporated herein by reference. , 6-TDI and 2,4-TDI are contacted with MCM-22 type molecular sieve of this invention which has been cation exchanged with K ions to adsorb 2,6-TDI, and then toluene is added. The 2,6-TDI is desorbed and recovered with the desorbent included.
(Xv) an adsorbent that separates 2,4TDI from isomers, as in US Pat. No. 4,721,807, which is incorporated herein by reference, and 2,6-TDI and 2,4-TDI Contacting the feed mixture comprising a MCM-22 type molecular sieve of the present invention cation exchanged with Na, Ca, Li and / or Mg ions to adsorb 2,6-TDI, and then a desorbent comprising toluene 2. Desorb and recover 2,4-TDI.
(Xvi) A process for reducing a durene component contained in a bottom fraction at 90 to 200 ° C., which is produced when methanol is catalytically converted to gasoline, which comprises MCM-22 type molecular sieve and hydrogenation of the present invention The bottom fraction containing durene is brought into contact with hydrogen in the presence of a catalyst containing a component metal, and the reaction conditions are any one of a temperature of about 230 ° C. to about 425 ° C. and a pressure of about 457 to about 22000 kPa-a. One or a combination.

In one embodiment, the crystalline molecular sieve of this invention, preferably an MCM-22 type molecular sieve, alkylates benzene, then produces and cleaves the alkylbenzene hydroperoxide to produce benzene and ketone, Can be used in the process of co-production of ketones.
In this process, the crystalline molecular sieve of this invention, preferably MCM-22 type molecular sieve, is used in the first stage, ie, the alkylation of benzene.

Examples Examples of such processes, examples of benzene and propylene are converted to phenol and acetone, for example as in the international application PCT / EP2005 / 008557, benzene and C ₄ olefins are converted to phenol and methyl ethyl ketone, benzene , Propylene, and C ₄ olefins are converted to phenol, acetone, and methyl ethyl ketone, in which case phenol and acetone are converted to bisphenol-A as in international application PCT / EP2005 / 008554, and benzene is Examples include conversion to phenol and cyclohexanone, or benzene and ethylene to phenol and methyl ethyl ketone, for example PCT / EP2OO5 / 008551.

The crystalline molecular sieve of this invention, preferably the MCM-22 type molecular sieve, is useful for the alkylation reaction of benzene, and in this case, selectivity to the alkylbenzene is required.
Furthermore, the crystalline molecular sieve of the present invention, preferably MCM-22 family molecular sieve, as in the international application PCT / EP2005 / 008557, selectively sec- butylbenzene from _{C 4} olefins and benzene rich in linear butenes It is particularly useful in manufacturing.

Preferably, the conversion reaction supplies benzene and C ₄ olefins to the catalyst of the invention, has a temperature of about 60 ° C. to about 260 ° C., such as about 100 ° C. to 200 ° C., a pressure of 7000 kPa-a or less, C It is carried out under conditions where the weight hourly space velocity (WHSV) based on a _4- alkylating agent is about 0.1 to 50 hr ⁻¹ and the molar ratio of benzene to C ₄ alkylating agent is about 1 to about 50.

  The crystalline molecular sieve of the present invention, preferably MCM-22 type molecular sieve, is also useful as a catalyst for an alkyl transfer reaction such as an alkyl transfer reaction of polyalkylbenzene.

For many catalysts, it is preferred to use the novel crystalline material in combination with another material that can withstand the temperature and other reaction conditions used in organic conversion processes. Such materials include active or inactive materials, or synthetic or naturally derived zeolites or inorganic materials such as metal oxides such as clay, silica, and / or alumina. The latter is naturally occurring or is a gelatinous sediment or gel-like form containing a mixture of silica and metal oxide.
When such materials are used with new crystalline materials, ie, when they are combined or combined when synthesizing new crystalline materials, in the case of active materials, in some organic conversion reactions, Conversion and / or selectivity may change.

The inert material acts as a diluent to control the conversion of a given process, and the product can be obtained economically and stably without using other means of controlling the reaction rate. .
These materials are combined with naturally derived clays such as bentonite and kaolin to improve the crush strength of the catalyst under commercial process operating conditions. Substances such as clay and oxide function as a binder for the catalyst. Commercially, it is desirable that the catalyst has high crushing strength because it is desirable to prevent the catalyst from being broken into powdery materials. Such clay binders have usually been used only to improve the crush strength of the catalyst.

  Naturally derived clays that are complexed with new crystalline materials include montmorillonites and kaolins, including suventnite, which is commonly used for Dixie, McNamie, Georgia, Florida Clay, and others The main mineral constituents are known as halloysite, kaolinite, dextite, narcosite, or anoxite. Such clays are used in the mined state or in the state of being baked, acid-treated or chemically modified. Binders useful for the crystalline material of the present invention further include inorganic oxides such as alumina.

  In addition to the above materials, the crystalline materials of the present invention include silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, and ternary silica-alumina-tria, silica -Composite with a porous base material such as alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia.

  The relative ratio between the finely dispersed crystalline molecular sieve and the inorganic oxide matrix can be in a wide range, and the content of crystalline material is about 1 to 99 wt%, usually when the composite is in the form of beads. Is contained in the composite from about 20 to about 80 wt%.

  Various aspects of the invention are illustrated by the following examples.

  In these examples, the XRD diffraction pattern of the unpurified material was recorded on a Bruker D4 X-Ray Powder Diffractometer using copper Kα radiation in the 2θ range 2 to 40 degrees.

  The SEM image was observed with Hitachi S4800 Field Emission Scanning Electron Microscope (SEM). The crystal size was determined from the average size of a plurality of crystals observed by SEM.

  Crystallinity was determined by multiplying the ratio of the sum of the two peaks at 7.1 and 26 (2θ) and the sum of the same peak of the standard sample (a reference sample with a given synthesis recipe and conditions) by 100.

  BET surface area was measured with a Micromeritics TriStar 3000 V6.05A (Micromeritics, Norcross, GA) after pre-treatment of the samples at 350 ° C. in air.

  The ratio of external surface area to total BET surface area was calculated from the t-plot obtained during BET measurement by nitrogen adsorption.

The electron diffraction pattern of the fired material of Example 4 was measured at 300 kV using a CM-30 transmission electron microscope from Philips / FEI (Einhoven, The Netherlands).
The diameter of the observation surface of the thin crystallites was 0.25 μm. The sample was ground in a mortar and then suspended by sonication in acetone and then applied onto a 300 mesh copper electron microscope grid coated with carbon film.
An electron microscope precession accessory (NanoMEGAS P010, Brussels, Belgium) was used to minimize the multiple scattering perturbation of the off-axis emission from the sample to the recorded intensity.

The diffraction pattern was recorded on a Fuji imaging plate and processed with a Microscanner from Ditabis (Pforzheim, Germany) to obtain a 16-bit digital image. The intensity of the diffraction pattern was integrated with the CRISP ELD program sold by Calidris (Sollentuna, Sweden).
In some cases, the tilt series of diffraction patterns (in most cases the hexagonal a ^* axis was used as the tilt axis) was determined from the eucentric goniometer stage of the electron microscope, and these The pattern was recorded on Kodak SO-163 electron microscope imaging film and developed with a Kodak HRP developer. After measuring the diffraction pattern, a three-dimensional representation of the reciprocal lattice showing the diffraction characteristics parallel to the c * axis was plotted.

The following examples are illustrative of preferred embodiments.
<Example A>
In this example, MCM-22 was prepared by the method disclosed in US Pat. No. 4,954,325.

Water, hexamethylenediamine (HMI) (Sigma-Aldrich), silica (Ultrasil®, Degussa), 45 wt% sodium aluminate solution (25.5% Al ₂ O ₃ , 19.5). Hydrothermal reaction mixture consisting of 50% Na ₂ O (USALCO) and 50 wt% sodium hydroxide solution. This mixture had the molar composition shown in Table VII.

  The hydrothermal reaction mixture was crystallized under the conditions shown in Table VII above. XRD of the crude material of Example A showed a pure MCM-22 phase. In the SEM image of the material of Example A, a plate-like form having an average crystal size of 0.5 × 0.025 μm was observed. An electron diffraction image of the calcined material of Example A is shown in FIG. 8a. After firing, this material exhibited the XRD pattern disclosed in US Pat. No. 4,954,325.

<Example 1 and Example 2>
Water, Me ₆ -Diquat-5 (“R”) dibromide (“SACHEM”), silica (Ultrasil®, Degussa), and aluminum sulfate (8.1% Al ₂ O ₃ ) solution A hydrothermal reaction mixture consisting of 50 wt% sodium hydroxide solution was prepared. This mixture had the molar composition shown in Table VIII.

  The mixture of Example 1 was crystallized at 170 ° C. for 80 hours without stirring in a Teflon bottle. After crystallization, the hydrothermal reaction mixture slurry of Example 1 was filtered off. The unpurified material showed the XRD pattern shown in FIG.

  The mixture of Example 2 was crystallized in a Teflon (registered trademark) bottle for 220 hours at 160 ° C. without stirring. After crystallization, the hydrothermal reaction mixture slurry of Example 2 was filtered off. The unpurified material showed the XRD pattern shown in FIG.

  The crystalline molecular sieves of Examples 1 and 2 showed XRD diffraction of the pure phase of MCM-22 type molecular sieve. In the XRD diffraction of the crystalline molecular sieves of Examples 1 and 2, peaks with a lattice spacing d were observed at 13.18 ± 0.25Å and 12.33 ± 0.23Å. The peak intensity when the lattice spacing d was 13.18 ± 0.25Å was approximately equal to or greater than the peak intensity when the lattice spacing d was 12.33 ± 0.23Å.

  Further, in the XRD diffraction of the crystalline molecular sieves of Examples 1 and 2, peaks with a lattice spacing d were observed at 11.06 ± 0.18Å and 9.25 ± 0.13Å. The peak intensity when the lattice spacing d was 11.06 ± 0.18 ほ ぼ was almost equal to or greater than the peak strength when the lattice spacing d was 9.25 ± 0.13 Å. In addition, the peak at a lattice spacing d of 11.06 ± 0.18 and the peak at 9.25 ± 0.13 were non-separable peaks.

  Furthermore, the XRD diffraction of the crystalline molecular sieves of Examples 1 and 2 is characterized by showing the values shown in Table II or Table III.

<Example 3>
100 g of 1M ammonium nitrate solution was mixed with 13 g of the solid of Example 1 (washed and dried). The mixture was stirred at room temperature (˜25 ° C.) for 1 hour and filtered off. The solid separated by this operation was further mixed with 100 g of 1M ammonium nitrate solution and stirred at room temperature (˜25 ° C.) for 1 hour. The mixture was filtered and washed with water. The solid separated by filtration and washed with water was dried in an oven at 110 ° C. for 24 hours.

<Example 4>
The synthesis was performed in the same manner as in Example 1 except that the crystallization time was 60 hours. A small sample was completely crystalline. After adding 400 milliliters of water to the slurry and stirring to allow the solids to settle, the supernatant was decanted off. Water was added again and stirred, and the slurry was filtered and washed with water. The resulting crude solid was dried at 121 ° C. (250 ° F.).

15 g of the crude product was ion-exchanged with 100 g of ammonium nitrate in the same manner as in Example 3. A portion of the ammonium exchanged material was calcined at 540 ° C. in air. The calcined product had a BET surface area of 514 m ² / g, an external surface area of 72 m ² / g, and a ratio of external surface area to total surface area of about 0.14.

  FIG. 7 shows the X-ray diffraction pattern of the material of Example 4 after being purified, after ammonium exchange, and after calcination.

The calcined MCM-22 type material (Comparative Example A), which is an example of a known unit cell, was hexagonal, space group P6 / mmm, a = about 14.21 Å, c = about 24.94 Å. .
When projected along the [001] axis, a sharp spot is observed in the hk0 pattern (FIG. 8A).
The amplitude data of a plurality of separated patterns for a lump of microcrystalline flakes satisfied the following relationship.
R = Σ || F (1) | −k | F (2) || / Σ | F (1) | ≦ 0.12
Here, k is normalized so that Σ | F (1) | = Σ | F (2) |, and | F (1) | and | F (2) | are comparisons of a plurality of separated patterns. The amplitude of the possible diffraction peak. A reciprocal lattice plot (FIG. 9a) with a tilt series of such a pattern shows that the spacing in the c-axis direction is approximately 25 mm.

On the other hand, a plot of the crystallite slope of a known MCM-22 precursor (Comparative Example A) (FIG. 9b) shows no lattice repetition in the c-axis direction (ie discontinuous reflection along c ^*). ), Showing a continuous streak of reflections. This result is consistent with the known Fourier transform of the single unit cell in the c-axis direction.

  The main hk0 electron diffraction pattern of the fired material of the present application is almost arc-shaped (FIG. 8C) in most cases, but is a spot pattern similar to the known MCM-22 material (Comparative Example A). A trace amount of impurities (compared to FIGS. 8B and 8A) was observed. The amplitude data of the pattern of a small number of spots was consistent with the known calcined MCM-22 material (R = 0.09).

The arc-shaped pattern did not match very much (R = 0.14) even though the matching in the inside was good (R <0.12).
Applying phenomenological Lorentz correction to the new material to correct the arc-shaped reflection (R = 0.12) improved the consistency of these two patterns.
From the three-dimensional tilt of the calcined material of the invention (Example 4, Fig. 9c), not only the reflection streaks along the c-axis (c ^* ) but also doubled cells repeated in this direction Was observed (see arrow in FIG. 9c).

The diffraction data of the crystalline molecular sieve of this invention (Example 4) shows that the structure of the basic unit cell of this material is the crystalline molecular sieve of the unit cell of a known calcined MCM-22 type material (Comparative Example A). It shows that it is not different from the structure of.
However, the crystalline molecular sieve of this invention (Example 4 ) differs from the crystalline molecular sieve of the known MCM-22 type material (Comparative Example A) in the following points.
(I) The layered structure of unit cells in the c-axis direction is broken so as to be supported by the streak of the diffraction pattern along the ( ^* c) direction in the arc-shaped hk0 pattern and / or the inclination of the microcrystal And / or (ii) c-doubled cells along the axial direction.

On the other hand, the known calcined MCM-22 type crystalline molecular sieve (Comparative Example A) has a regular laminated structure along the c-axis direction and has regular crystallinity in all directions.
The arc-shaped and streak-shaped electron diffraction pattern of the crystalline molecular sieve of the present invention (Example 4) also confirms that the line becomes broad in the powder X-ray diffraction pattern.

<Example 5>
A catalyst was prepared by mixing 80 parts by weight of the product of Example 1 and 20 parts by weight of alumina (LaRoche Versal 300) on a dry weight basis. The catalyst was slurried with ammonium nitrate, filtered off and dried at 120 ° C. before use. The catalyst was calcined at 540 ° C. in nitrogen, then ion-exchanged with an aqueous ammonium nitrate solution and activated by calcining at 540 ° C. in air.

<Example 6>
A catalyst was prepared by mixing 80 parts by weight of Comparative Example A and 20 parts by weight of alumina (LaRoche Versal 300) on a dry weight basis. Water was added to the mixture to form an extruded shape. This extruded shaped product was dried at 120 ° C. before use. The catalyst was calcined at 540 ° C. in nitrogen, then ion-exchanged with an aqueous ammonium nitrate solution and activated by calcining at 540 ° C. in air.

<Example 7>
The catalyst size of Example 5 and Example 6 was adjusted to 14/24 mesh, and a test for alkylation of benzene with propylene was conducted. Alkylation of benzene with propylene was carried out using the catalysts of Examples 5 and 6. The catalyst was placed in a catalyst basket and placed in a Parr autoclave reactor. Benzene (156.1 g) and propylene (28.1 g) were added so that the molar ratio of benzene: propylene was 3: 1. The reaction conditions were 130 ° C. and 2138 kPa-a (300 psig), and the reaction was carried out for 4 hours. Periodically, small samples of the product were withdrawn and analyzed using off-line GC (Model HP 5890). The performance of the catalyst was evaluated by a kinetic activity constant based on the conversion rate of propylene and the selectivity for cumene when the conversion rate of propylene was 100%.

  The activity and selectivity test results of Example 5 are shown normalized to the catalyst of Example 6. These results are shown in Table IX below.

  The catalyst of the present application showed activity and selectivity for the alkylation reaction of benzene.

  Although the present invention has been described based on the embodiments, those skilled in the art will be able to make various changes and modifications based on the matters disclosed in the specification without departing from the essence of the present invention. Therefore, the scope of the present invention is not limited to the embodiments, and based on the description of the claims, all novel and patentable characteristics disclosed in the present application, including a scope recognized by those skilled in the art as equivalent to the present invention, are included. Some items are included.

Claims (7)

Ammonia exchange or calcination comprising unit cells of MWW topology, identified by c-axis-direction unit cell stack structure collapsed, and electron diffraction streak from c-axis direction unit cell array A crystalline molecular sieve in a formed form ,
A crystalline molecular sieve, wherein the crystalline molecular sieve is further identified by an arc-shaped hk0 pattern of an electron diffraction pattern or by a double unit cell in the c-axis direction . The crystalline molecular sieve according to claim 1 , wherein the total surface area measured by the nitrogen adsorption BET method exceeds 450 m ² / g. The external surface area / total surface area ratio after conversion to H-type by ion exchange with ammonium nitrate and calcination is less than 0.15, wherein the external surface area is determined by a t-plot of a nitrogen adsorption BET method. 2. The crystalline molecular sieve according to 2. The crystalline molecular sieve according to claim 1, wherein the crystalline molecular sieve has a plate-like form and at least 50 wt% of the crystalline molecular sieve has a crystal diameter of more than 1 μm as measured by SEM. The crystalline molecular sieve according to claim 4 , wherein the crystalline molecular sieve is in the form of a plate agglomerate, wherein at least 50 wt% of the crystalline molecular sieve has a crystal thickness of 0.025 μm as measured by SEM. A method for producing a crystalline molecular sieve, comprising:
(A) at least one source of at least one tetravalent element (Y), at least one source of at least one alkali metal or alkaline earth metal, and at least one structural regulator (R) Supplying a mixture comprising water and optionally at least one source of at least one trivalent element (X), wherein the mixture has the following molar composition ratio:
Y: X ₂ = 10 to infinity;
H ₂ O: Y = 5 to 35;
OH ⁻ : Y = 0.001 to 2;
M ⁺ : Y = 0.001 to 2;
R: Y = 0.001 to 2;
(Where M is an alkali metal and R is one of N, N, N, N′N′N′-hexamethyl-1,5-pentanediaminium salts (Me ₆ -Diquat-5 salts)), The molar composition ratio of OH ⁻ : Y is the total number of moles of net OH ⁻ groups obtained by subtracting the number of moles of OH ⁻ groups consumed according to the type of trivalent element source from the total number of moles of OH ⁻ groups added. Obtained using
(B) A step of producing a product containing a desired crystalline molecular sieve under crystallization conditions, wherein the temperature is 100 ° C. to 200 ° C., and the crystallization time is 1 hour to 400 hours. A step involving being; and
(C) recovering the crystalline molecular sieve;
(D) The recovered crystalline molecular sieve is
(1) ion-exchange the crystalline molecular sieve with an ammonium salt solution;
(2) firing the crystalline molecular sieve under firing conditions; or (3) treating the crystalline molecular sieve by ion exchange with an ammonium salt solution and firing under firing conditions. A method for producing a crystalline molecular sieve. A method for converting hydrocarbons, (a) a hydrocarbon feedstock, the crystalline molecular sieve according to claims 1 to 5, and the crystalline molecular sieve produced by the method according to claim 6 A method for converting hydrocarbons comprising the step of contacting a crystalline molecular sieve of any of the above under a conversion condition to produce a converted product.

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